Electroconductive article and production thereof



Patented Nov. 11, 1952 ELECTROCONDUCTIVE ARTICLE AND PRODUCTION THEREOF William 0. Lytle, New Kensingtom P-a", 'assignor to Pittsburgh Plate Glass Company; Allegheny :County, Pa., a corporation of Pennsylvania No Drawing. Application December 19,1951,

Serial No. 262,471

13 Claims. (01. 117-44) This invention relates 'to the production of transparent films or coatings upon lime soda glassandto novel glass products havingelectroconductive coatings. In United States-Letters Patent No. 2,118,795granted to J. T. Littleton, a process is described wherein an electroconductive coating is deposited upon a glass insulator by heating the insulator to a temperature of 600' to 750 C. and subjecting'the hot insulator to "the action of--stannic chloride. The films thus'deposite'dare stated to be iridescent and transparentto solar heat and are said to im' provethe properties of insulators.

Since such films possess some transparency,

. attempts have been made to apply them to transparentplateor window glass sheets to be used'as viewing closures and to make use of the conducti'vefilmas heating elements in an electrical circuit-inorder to heat the glass and thus to prevent orminimize formation of fog, snow or ice thereupon. However, serious problems arise from such attempts. If the films are deposited, according to the process of the abovepatent at "a temperature of about 1100-1150 F. or below, in a thickness sufficient to give the film a relatively high electrocondu-ctivity so that a relatively low voltage, for example 6 110220 volts, may be applied effectively thereto, the films frequently have poor transparency and may even be opaque. On the other hand,'films which aresu'mciently thin to have good transparency often have electrical resistance well above 1000 to 2000 ohms per unit square. While some improvement is possible at higher temperatures, treatment of soda lime glass except in thick sections becomes objectionable because of the tendency of the glass to soften objectionably. The expression of electrical resistance in terms of ohms per unit square is a convenient method of expressing the resistance of thin films and in reality is the specific resistivity of the film divided by the average film thickness within the area of a square.

Further research has led to the discovery that by use of proper precautions and special solutions, transparent films can be provided on soda lime glass which have unusually low electrical resistance. Thus, it has been found that the use of certain agents such as'methanol or phenyl hydrazine hydrochloride in conjunction with stannic chloride produces a transparent coating which has a resistance in terms of ohms per unit square below500and generally below 150. Such low electrical resistance has made possible the provision of viewing closures in the cabins of automotive vehicles'such as'aircraft and automobiles which f'have a transpare'nt surface which closures maybe electricallyheated i'nua convenlent manner. The provision of-such' ianarticle affords a :convenientiimeans of preveritingfiaccumulation ofxiog, ice :=or snow upon the viewing closure; simply by electrically heating: the -glass,

kali metal migrate to the surface and the surface usingltheitransparent filmsas theresistanceclement.

Desiptethe l fact that the above :p'rocess per-- mits production on-alarge scale of 'vi'ewingclosures having conductive films with electrical-resistancebelow 500 ohms iper-unit square, a por-- tion of: products thus produced have been defective due to thepresence of haze in the film. This haze sometimes developedin localizedareas of the glass sheet-and at other times.'the entire surface of certain articles was found to be hazy. In consequence, an unduenumberof glass panels have been rejected-as unsuitable for use as viewingclosures. I Losses dueto these"rejects have very'materially increasedthe cost of production of suit-ableviewing closures.

According to the present invention, it has been found that hazeand similar defects maybe eliminated or substantially reduced by providing between'the base andthe electroconductive coating an intermediate layer, "film or coating a refractory transparent metal oxide material or like refractory material'which either is free of NazO or which'has acontentof available Na'2O lower than that of the surface o'fsoda lime glass which hasbeenhe'ated for one or sever'al minutes to" the temperature at which'the electroconductive coating is 'to be'ap'plied (usually above 400 'F.,for example "1150"'F.). Preferably the NazO content ofthe surface'if present should be'below that of the interior 'of'the soda lime glass.

"The reduction in haze which accrues by virtue of this process is enacted by restricting the amount df "alkali metal which is permitted to come into contact-with the electroconductive film duringformation. lt will be understood that'ordinarysuda' lime glass contains a certain minimumoialkali metal as NaiO and K20. When such 'glass is heated, for example above 400 'F.

for'onepr-moreminutes further amounts of alconcentration "thereofi becomes quite high. Hence as "stannicchloride or similar compound is'applie'd to thebase'alkali metal salt is formed and becomes entrapped in the coating being i formed thus'causing'haze. 'The intermediate"surfaceffilm or'layer restrains "migration of "the alkali metal. Consequently haze "formation will'be minimized if the intermediate film contains no alkali metal or at 1 least less 'alkalimetal (K2O and'NazO for ex ampler-than does theglass surface'after heating to the temperature at which" the electroconductive film isiapplied.

- In the-usual practice of the invention, 'the' glass is cleaned andcoated with 'athen transparent layer 'of'the refractory coating. Thisfilm -is quite. thin, :usually having; a thickness below 100 millimicrons wid -rarely being above 300 mil-limicrons; Whera-sheetsvofglass are treated,-it' is advantageous' toacapplynor"form the film upon 3 both sides of the glass in order to avoid any tendency toward Warping during the subsequent coating operation.

Following this coating operation, the glass is heated above 400 F., preferably 800 to 1250 F. and the heated sheet is sprayed or otherwise contacted with an hydrolyzable metal compound, such as stannic chloride, which is capable of producing a transparent electroconductive coating upon the treated surface of the glass, usually upon one side of the sheet. Care should be exerted to avoid an excessively long heating period since alkali metal in the interior of the glass tends to migrate to the surface through the refractory layer to an objectionable degree thus causing haze formation. Consequently, heating should be discontinued and the electroconductive film should be applied before such migration can occur to adegree such as to raise the alkali metal atom concentration at the surface of the silica coating to the point where the NazO content of the coating is substantially that of untreated glass when heated to the same temperature.

This invention is applicable to use in connection with the treatment of window glass or plate glass, i. e. soda lime glass, since haze which develops due to the presence of alkali does not appear to be serious With other forms of glass. Furthermore, it is of particular importance when metal halides, such as stannic chloride, are used to form or deposit the transparent electroconductive-film.

Various refractory compositions may be applied according to this invention. In general, suitable refractory films may be applied by spraying the glass at a temperature of 800 to 1250 F. with a saturated or other relatively concentrated aqueous solution of a soluble salt of copper, aluminum, lead, zinc, iron, nickel, cobalt, thallium or silver. Clearest films are obtained using the acetates of these metals. However, the chlorides, bromides, iodides, nitrates, and nitriles also may be used. For example, a coating, believed to comprise silver oxide, may be applied by sprayingglass heated to a temperature above about 400 F., for example, 800 to 1250 F., with a saturated aqueous silver nitrate solution. Coatings of'aluminum oxide may be applied in a similar way'by spraying with an aqueous solution of an aluminum salt, such as aluminum chloride, acetate,'bromide or nitrate. Similar results may be obtained using saturated salts of aqueous solutions of antimony trichloride or pentachloride. Boron-containing films may be applied by spraying the hot glass with boron trifiuoride or boric acid.

Titanium films may be deposited by dipping the glassin titanium tetrachloride or the reaction product obtained by mixing titanium tetrachloride with 2-10 per cent by weight of ethyl alcohol or an equivalent amount of lower aliphatic alcohol containing up to 5 carbon atoms. They may also be provided by spraying glass heated to about 220 C. with tetanium tetrachloride in atmospheric air.

The exact composition of the intermediate film provided is not known with absolute certainty and is diiiicult to determine because of its thinness. Usually it comprises an oxygen compound,

i. e. an oxide of the metal used. which may or may not be in combination with silica.

above about 400 usually 800 to 1250 F., but below the temperature at which the glass melts. The'heated glass is sprayed with the metal compound such'as stannic chloride (usually in all The treated glass is heated to a temperature which possesses some amount of moisture characteristic of atmospheric air). The period of heating should be limited since, if heating is continued for an excessive period migration of alkali metal atoms from the interior of the glass through the silica film tends to occur thereby nullifying the effect of the silica film. Usually, a heating period of 1 to 10 minutes is sufficient for the purpose. Longer times are permissible so long as the amount of alkali metal diffusion does not become excessive, but rarely is heating continued over one hour.

When the glass has been heated to the above temperature, it is withdrawn from the heating zone and immediately is sprayed in atmospheric air of natural humidity (usually 30 percent or above) with the coating compound either as a vapor or solution. When a solution is used, a quantity of the coating solution is placed in an atomizing spray gun and the hot glass'is sprayed with an atomized spray of the solution for a few seconds, usually of the order of 1 to 20 seconds. Usually this coating operation is conducted in the presence of an oxygen source such as water, air or oxygen. Conductive coatings have been obtained when air did not appear to be present although it is probable that oxygen available either as elemental oxygen or combined in water or similar compound is essential to this operation.

When a tin compound, such as stannic chloride, stannous chloride, stannous acetate, stannous phosphate, stannis phosphate, stannous oxalate or equivalent hydrolyzable tin compound, is used as the coating material, the process produces a transparent electroconductive film which largely comprises an oxide of tin. Such films are at least -99 percent tin oxide and contain certain impurities such as chlorine, carbon and silicon, together with some amount of elemental tin.

In depositing films upon soda lime glass, it has been found that certain agents, notably methanol and phenyl hydrazine hydrochloride or antimony trichloride materially improve the coating particularly as to its electroconductivity. A wide variety of other agents of this character such as those described in an application of W. O. Lytle for United States Letters Patent, Serial No. 762,658, filed July 22, 1947 may be used.

The amount of the addition agent which is used is capable of substantial variation depending upon the results desired. Small amounts (even traces) show an improvement in the conductivity and freedom from haze of the film and such improvement increases to a maximum as the amount of addition agent is increased. In general the amount of such agent which is used in conjunction with the tin compound at least 0.01 to 0.1 mol per mol of tin compound. As an example, with agents such as methanol it has been found that a solution comprising 1000 parts by weight of SnCl4-5HzO and 1 part by wei ht of methanol produced a film having a specific resistivity of about 0.012 ohm centimeter, whereas a solution containing equal parts by weight of stannic chloride pentahydrate and methanol produced a film having a specific resistivity below 0.002. Since larger amounts of such agents do not produce markedly greater improvement of the film, it is quite rare to use more than 50 parts by weight of addition agent per part by weight of tin compound.

Quite frequently, mixtures of agents have been found to be preferable. For example, alcohols such as methanol or. others above listed" are ,5 :founditoifunctiontbetter whemused withihydrazines such" asphejnyh hydrazine orrphenylr hydra- :zinehydrochloride n01: the; other hydrazines; .or their hydrochlorides. :rInsuch, a case ateleast .;0.0 1 :mol of -the hydrazine Y'such. as -phenyl Qhydrazine and 50101 mol ofethe salcoholwsuch @a's nillGlihfiIlOl, per mol of tin: compoundisu'ch:asistannic chloride normally-areyused.

invention ihaswbeeni-described "with ;-special 'reference,:ato the. use ot-:- stanniclich-loride asfthe tin compound ,"for production ,of the *electroconductive ,ifilm. "This-@zcompound: is .-r:particularly valuablelsince it .;may be: .usedceith'er in aqueous medium robin :vaponstate to DLOdUCGifiIIBS X-Vhifih visibly appearltorbel flawless. L :Obher;fi'1m torming .atin (partieularlyacompoundswhich: are shyldrojlyzable more decomposable toil produce -a tin oxide;.electroconductive ccoating) tare useful :tor this purpose. :lEhus,=- compounds;-suchaas-stannic nice-sulphate StQIHI QLPhOSILhaItB, -stannic nitrate or stannous lsaltsesuchaas stannous acetate, v stanno-u-s oxalatacstannouschloride, stannousin-itrate, stannous tartarate or stannous phosphatezmay be used. Organic tin icompoundstalso mayvbe used. suchrcompoundstinclude, those 1 having the-structureMRmSnXwWhere-"Bus .a monovalent aryl, aliphatic,tor varyl-aliphatic-radical1 linkedto the .tin atom through carbonland: X is; another monovalent laryl, galiphatic-l or? aryl-al-iphatic radical linked to: the "tin-atom through-carbon or ,is .a radical such as hydroxyl, chloride tbromide, iodine, etcsand the sumvof m and n is insurmas tetra zfithyh tin, tetra methyl tin, ,-tetra.--n-heptyl tin, itetrabenzylitin tetra \phenyltin,.tetra-p-to1y1 tin,. .rtetr-ar-p-xylyl ,tin, l-tribenzyl ethyl .tin, tribenzyl-itin 'ChIOIlGE tIibUtYL-UII chloride, ,triethyln-amyltin, tolyl tin-trichloride,.-.ethylvtinatri bromide, =ethyl vstannici. acid, ethyll ,chlorostannic acid, diethyl tinioxide. "Moreover,. other, tin compounds such as diphenyl; tin; .diethyltin, stannic. .bis-acetylacetone dichloride ,or 'clibromide, etc, maybe fused.

In general it is, desired touse tin compounds ivhichiarediqu'id or which -..may be vaporized readily .or which mayfllbe dissolved in solvents such as Water'or organic solventsjsuch asbeln zene, xylene, toluene,.acetone, methanol ethanol, methyl ethyl ketone, etc.; -in order'that the tin compound may be sapplied' to the base as a homogeneous. liquid or solution. Such solutions normally containat least'loito 5;) parts byrweight of tin compound per I partsby"weight'offsolution.

According to a-further embodiment mixed oxides may be applied. For example; ZJYfiCYJlSOllS solution containing" the usual" amount of staniziic chlorideorJother tin compound may have dissOIVe'dLtherein or mixed therewith compoundsiof other metalssuch as indiumchloride,cadmium bromide, "cadmium; acetate; zinc" bromide, zinc acetate; thallium "nitrate, "chromium chloride, ferricv chloride or .other:compoundof (these; metals to modifyth'etproperties of .the film. e As :a'atypieal. embodiment lo to 500 perc,ent byvweight or" hallium initrate :or i cadmium i'chloride-wor acetate based upon'ithe 'weightpf stannic chloride in-the solution may be added wto theqsolutionswof Examples l 2, 3 or 4 adding suflicient water if neocssary to dissolve the mixture anda-these solutions may housed in lieu of the solutions-described in such examples.

Not infrequently, it is desirable to apply the transparent coating to' the -dealkalized glass Jbase by recourseito '-.a -va'porized tin compoundssuchias stan-riic" chlori'de vapor. lnisuclnafcase the vapor the vapor :mixture sprayedupon 1 the glass. base.

v.JDuring the a coating: operation" whether i by: use ,oiaanhydrous vapor a or-eaqueous solution of lthe tinrcompound the hot glass normally is -supported,- by convenient means 'in atmospheric" air which normally contains somemoisture- (relative humidity usually above -30 -percent). zConsequentlythe spraying operation is conducted in thepresenceof waterreven if no'water'isvpresent in, the 1 spray itself.

Sinceathe. haze whichiis avoided by recourse to this invention is largely created by sodium, :the invention is applicable ,to the provision of, electroconductive -.coating-....and upon various types ,of glass "having a high sodium. content. {Ifhese glasses have the composition:

Alkali zmetal oxide .su'ch as j Na O and/or K20 .J.0 ,to 35%. byweight Alkaline earth metal oxide -:,suchwasLClO:a1id/orMgO;: "moi- 25% ":by '*weight the G content ebeing ,"not less than "5%Iby weight 'SiO c; '5 01t0"7'5%--by-aveight A1203 7 l .0 tobyi weight It-Will be understood that various other ma- 'terials, usually-in small amount (l-to 5% by weight or-less) also maybe present. such materials include arsenic, antimony fluorine, lithiumybalrium; zinc, titanium; B203, iron, cobalt, nickel; lead, phosphate and'the like.

'As previously stated, the invention has" been foundtobe especially valuable when used in the coating of window and plate glass which are made of limes'oda glass. "Such glass usually has the following compositions:

Alkali metal oxide such as IigOiilld/Ol Na O 10 to l8%-'byweight Alkaline rearth "metal :oxide -such as MgO and/or CaO -5 to 16% by weight the 0:10 'content" being at least '5 /0" by weight to %,.byweight 0 to 5% by weight Si 0 A1 0 Atypicallime soda glass used as window glass has the. following composition:

SiO 71.38% byweight ('usualvariation 7] vt0v.73% by Weight) N0 0 12.79% by Weight (usual variation 12 to 14% by weight) CaO' -9.(37%' by weight (usual variation 8 to 11% by'vveight) 33% by Weight '.7 5 by weight .12 by weight 315% byweight 0.81%'by Weight Othernertinent properties of these-electroconductiveifilms on lime soda'glass are:

lvlobilityicmi /volt second 8 No. ionized impurity centerslper cm. About "10 Mean 'freehp'ath of. current carriersl Aboutf'S 10- cm. Index of "refraction of film About? Hazafactor vBelowi2i5 Resistivity Below 01005, ohm-a-cm.

7. 1944, part 3, pages 1653-5, American Society Testing Materials, New York.

The color characteristics of the coating are determined to a substantial degree by the thickness of the coating. Colorless coatings may be obtained by use of tin oxide or similar coatings which are below about '75 to 100 millimicrons in thickness. Thicker coatings having a thickness of '75 to 600 microns possess a color depending upon the exact thickness. The exact thickness of the film depends upon the number of coatings and/or the length of time of spraying. In general, the film thickness will not be in excess of 800 microns.

It will be understood that the article which is produced as described above comprises a soda lime glassbase, a transparent electroconductive coating on the base and an intermediate metal oxide layer, film or coating between the base and the electroconductive coating.

. V The available NazO and equivalent alkali metal oxide content of the metal oxide should in no case exceed that of ordinary untreated soda lime glass after heating the untreated glass at an elevated temperature, for example 1150 F. for a period of 4 minutes (or such other time and temperature tobe used for heating the glass to the temperature at which the electroconductive film is to be applied). Obviously the film may even be free of alkali metal. However, it should be noted that improvement may be observed through use of films which contain more NazO or equivalent alkali metal than ordinary unheated soda lime glass so long as the available NazO content is below that of glass which has been heated after formation into sheet or similar product to the temperature at which the electroconductive coating is supplied. Thus it has been found that when plate glass samples, 6 inches by 6 inches by inch were immersed in 350 cubic centimeters of water for two hours, the amount of NazO which is dissolved in the solution amounts to about 0.05 to 0.4 milligram per square foot of glass surface. On the other hand, when such plates are heated for 4 minutes at 1150 F. and immersed in 350 cubic centimeters of water as above, the NaeO content of the Water amounts to from about 1.5 to as high as 3 (the average being about 2) milligrams per square foot of glass surface.

From the above test it will be apparent that films which exhibit available NazO contents according to this test below 1.5 milligrams per square foot should be used. Even films which contain NazO, such as those formed from aqueous sodium silicate of the composition NazOlSiOz); where a: is greater than 3, will effect an improvement in some cases.

The above test affords a convenient method for comparing the available NazO content of glass with glass provided with the film herein. contemplated. Samples of uncoated glass and coated glass may be heated in a furnace at the temperature for example 1150 F., and for the time for example 4 minutes, to be used in the application of the electroconductive coating. These samples then may be cooled and their surface NazO content compared as described above. If the Na2O content of the coated glass sample is found to be lower than that of the untreated glass sample after such heating, the treated glass will, in general, afford improvement as to haze.

In general, appreciable improvement is obtained when the glass to be coated with the electroconductive film exhibits available surface NazO determined as described above is less than 1 milligram and preferably less than 0.5 milligram per square foot of glass surface. The intermediate films produced according to methods herein described usually exhibit available NazO contents of 0.05 to 0.4 milligram per square foot even after the glass provided with the film has been heated at 1150 F. for 4 minutes.

These intermediate films or coatings may be separately defined layers or they may be essentially a continuation of the silica skeleton. Thus the term film as applied to these intermediate films refers to films which are deposited upon the base and those formed in situ. Consequently, the term is intended to include glass bases whereas the NazO content of the surface has been decreased by base exchange or analagous reaction. For example, when soda lime glass is heated at 800 F. or sprayed with vapors or solutions of metal halides such as ferric chloride or cuprous chloride. A film is formed which may exist as a definite layer or as a thin dealkalized surface zone extending from the outside into the interior of the glass without clear demarkation of layer formation.

As noted above, when sheets are treated, it is preferred to apply the metal oxide film to both sides of the sheet to prevent warping during the subsequent application of the electroconductive film. The electroconductive film normally is deposited upon but a single side of the treated surface although it may be applied upon both sides if desired.

The above description has been primarily directed to provision of articles having transparent tin oxide electroconductive films. However, the invention is applicable to transparent electroconductive films generally, all of such films being essentially equivalent. Thus transparent electroconductive films of cadmium oxide or indium oxide may be provided by use of cadmium or indium acetate, chloride or bromide in lieu of stannic chloride. Moreover, mixtures of these compounds with tin chloride or antimony chloride or with themselves may be used. Such coatings largely comprise the oxide or mixed oxide corresponding to the metal compound or compounds applied.

The following examples are illustrative:

Example 1 A glass plate is dipped in a solution prepared by adding 5 percent by weight of titanium tetrachloride to ethyl alcohol and cooling the mixture thus obtained. The dipped glass is allowed to dry and is cleaned.

This treated glass is vertically suspended, narrow sides being in a horizontal plane, and is heated in a furnacechamber at a temperature of 1150 F. for 3 minutes. A conventional spray gun is filled with a solution prepared by mixing the following components in the proportions:

stannic chloride pentahydrate gramsw 900 Methano1 milliliters 63 Phenyl hydrazine grams 21 Dioctyl sodium s u l f o s u c c in a t e solution milliliters 30 This solution is composed of Dioctyl sodium sulfosuccinate grams 10 Methano1 do 45 Water do- 45 The spray gun is turned on and the stannic chloride solution is sprayed evenly upon the hot glass by holding the glass vertically with its front face perpendicular to the spray no'zzle and"movingithe glass across the spray so that the-"gun "is" directed at apoint= midway-between the top and bottom edges ofthe-she'etz" If-neces--- saryfseveral gunsmountewone abovethe other may be usedto" apply" the coating.

The-rate of' movingthe"sheet across the*-sprayis such as to require"approximately fi" seconds -tomove a sheet 17 inches by 25 1 inches :z'entirely throughtthespray. 1 During this periodapproximately 20 cc. of solution isesprayedm Followingthe spraying operation, the sheet istempered-to atemper ofiapproximately one fourththat of run temper? The-resulting sheet has-a..clear.. transparent 15 iridescent tin oxide coating which i has 7 a resiistivityof approximately 125 -ohmsperunit squares The thickness of theelectroconductive coating ,is' 300-400 millimicrons.

Erample -z An aqueoussolu'tion is prepared byldissolving (4 grams of stannousaceta'te and, 30mil1il'iters of methanol'lin. enough 12Fnormal aqueous hydrochloriclacid .to' cause the stannous acetate todislsolve. .This solution is'liallowed. to age by. stand-l" ing l overnight.

A glass plate, 8 inches by .4inches by /647 inch is treated with a titanium tetrachlorid'e'as in ampleland isheated inla furnace chamberhav m a'teinperatureof 1250??? for 2%minutes; 5 milliliters ofthe aged solution is sprayed in 5sec-" 011615 from a conventional atomizingspray gun? on the heated glass immediatlyafteritsremoval" from the furnace.

Example .3

A small soda lime glasstplatet-washeated! for 2 /g minutes :in a: furnace chamber ata temperature ofi 'll50 rFl This hot sheet was sprayed for 2.5 secondsv at 40" pounds persquare inch' pressure hi0 usingla conventional spray gun with an aqueous solution containing 20percent *byweight of" silver nitrateandfipe'rcent'by'weight of aqueous form aldehyde containing" 40' percentby weight of fcrmaldehyde'r'.

The"'treatedglass wasfcleaned.'and heatedat" 1150*.31 for-2V 'minutesand sprayed for"1;5 sec ondsiat' '40 pounds per square-"inchpressure usingafcon'ventiona1spray guri; with" asolutiompre pared'fas ;foll'ows:" t p Sven""grams "of "phenyl 1hydrazinemydrochlo' ride'was dissolved .in30milli1iters"of wateri' 300 grams" of stannic' chloride pentahydrate waw melted at l40"FZ""and the two" solutions-were mixed? Awery clearplate 'wasobtained w This process also maybe performed,:using the V stannic chloride solutionsofExample"1. Moreover, saturated aqueous solution a of aluminumi chloride, copper chloride, antimony chloride, cobalt chloride, nickel chloride,,ferrousnchloride I or zinc chloridemay 'be used-in--lieu--of: silver nitrate.

I Ina series-of tests, polished plate glass sheets 4 inches by 8 inches *by -inchwere heated roe 2 minutes at a furnace temperature of'1250 F." The-solutions having the composition indicated below-were made upand l5 grams of each solu-wg' 7 tion was sprayed up-cn trfe' nated lass plate and the plates were allowed to cool: 3

1. 20 grams vzinc acetate-.Zn(C2HaOz) 2.21120 50 grams water 5 gramsphenylhydrazine hydrochloride 2; grams-cadmium acetate --g-rams--water- I 3."20 grams" chromium acetate 'Crwzl-l Oi") iIIIEiO" -50-*g-ramswaterfl aobalt* acetate GOK-CEI-HGEJ241126 50 grams water? 6-. '10 :grams. aluminum acetate AliGEKCzHsI-Q) 4241-3220 25""mill' "trslfi normal "ammonium hydroxide; 7. 50 grams' lead acetatePbICzHOlZiiI-EGJ 100 rams water:

8m 30 grams nickel acetate =NMO2H3O2) zAHcOA 60 grams methanol Example 6 Solution of 40 grams of antimony trichloridei 20 milliliters of anhydrou'stmethan'ol 20 millilitersofconcentrated'hydrrochl'oriczacidi- (37 percent H01) 5; milliliterspf faqueous hydrogenperoxide containingnfiilwpercent:I-lIzOa was prepared. Glass sheets-Bd-nchesby-fi-inches by ta -inch were-"heated to; 800 Fnand sprayedri with .--the-above solution to produce a film iofrfirstc or second order viol'et: Theseesheetsidverewree heated to 1150 F. and -coated' -with itin" oxide b spraying with thei=stannic chloride solution de scribed fi-i-n: :Example 1. e Moreover; the followingk solution may. abewnsedr; in lieu of the tin solutions in any of the -"arrows examples-z 1. 2 parts by volume of a saturated aqueoussolu tion of cadmiumcbromide y 1 pa'rt by volume oranaqueous solutidnzfcdn taining 30 percent byweightc'ofi- Hzfim 2. :Aqueousindi um trichlorid solution contairrw met-1200 grams of-InGl3 per-liter? 3. .Saturated zlnClalso llltioniiin anhydrous met anol-- containingxl percent of: antimony chloride or aqueous 48 percent hydrofiuo ls-Saturated aqueous indium tree-eats 100 grams water.

The above described-tproducts are capableidofs: use Wherever transparency and electroconducting,v are desirable properties. Theyiaretespeciallylefifective' as win'd shiel'ds' or -ot-her.- viewingtfcldsures in vehicles such as automobilesman'd 1mm wh'1clifmay be constructedas'described'in uf application: forsgUnited States Letters Patent of willianffifliytleii erial -No:762;659;filed'"Ju1y.223

O 1947 disclosure of which is hereby incorporatedby,

A typical composition which may be used for this purpose is as follows:

Per cent by weight The glass with the applied bus bars may be treated according to any of the above examples. The resulting products may be used as windshields, electrical resistance elements, heating elements, instrument dials, etc.

Although the present invention has been described with reference to the specific details of certain embodiments thereof, it is not intended that such details shall be regarded as limitations upon the scope of the invention except insofar as included'in the accompanying claims.

Reference is made to copending applications, Serial Nos. 36,420 and 36,425, both filed July 1, 1948, and now forfeited.

This application is a continuation-in-part of my application Serial No. 36,435, filed July 1, 1948, and now forfeited.

I claim:

1. A transparent glass article which comprises a glass base having the composition:

Alkali metal oxide of the group consisting of M120 and K20 10 to 35% by weight Alkaline earth metal ox1de of the group consisting of CaO and MgO 5 to 25% by weight the CaO content being at 7 least 5% by weight S10 50 to 75% by weight A1 0 Up to by weight having a transparent tin oxide electroconductive coating upon the base and an intermediate transparent metal oxide layer between the base and the coating, the metal oxide of said intermediate layer being a member selected from the group consisting of the oxides of silver, aluminum, antimony, copper, iron, cobalt, nickel, thallium and zinc.

2. The article of claim 1 wherein the glass has the composition:

Alkalimetal oxide of the group consisting of M120 and 0&0

10 to 18% by weight Alkaline earth metal oxide of the group consisting of CaO and M20 5 to 16% .by weight S102 6a to 75% by weight A1203 Up to 5% by weight 10 to by weight 5 to 25% by weight the (3:10 content being at least 5% by weight SiOg 50 to 75% by weight A1203 Up to 20% by weight having a transparent electroconductive coating of an oxide of a metal of the group consisting of tin, cadmium and indium upon the base and an intermediate transparent metal oxide layer between the base and the coatings, the metal oxide of said intermediate layer being a member selected from the group consisting of the oxides of silver, aluminum, antimony, copper, iron, cobalt, nickel, thallium and zinc.

'7. A method of providing a substantially hazefree glass base having a transparent electroconductive coating thereon, which comprises heating a glass having the composition:

Alkali metal oxide of the group consisting of Nago and 20 10 to 35% by weight Alkaline earth metal oxide of the group consisting of (38.0 and MgO 5 to 25% by weight the C content being at least 5% by weight S102 50 to 75% by weight A1203 Up to 20% by weight to a. temperature of above about 400 F. but below a temperature at which the glass melts, contacting the hot glass with a film-forming decomposable salt of a metal selected from the group consisting of silver, aluminum, antimony, copper, iron, cobalt, nickel, thallium and zinc whereby to deposit a transparent coating of an oxide of a metal of said group upon a surface of the glass, heating the glass to a temperature above about 400 F. but below the temperature at which the glass melts, and contacting the hot glass with stannic chloride whereby to deposit a transparent electroconductive tin oxide coating upon a treated surface of the glass.

8. A method of providing a substantially hazefree glass base having a transparent electroconductive coating thereon, which comprises heating a, glass having the composition:

Alkali metal oxide of the group consisting of Na 0 and K20 Alkaline earth metal oxide of the group consisting of CaO and MgO 10 to 35% by weight 5 to 25% by weight the 09.0 content being at least 5% by weight 50 to 75% by weight Up to 20% by weight to a temperature of above about 400 F. but below a temperature at which the glass melts, contacting the hot glass with a film-forming decomposable salt of a metal selected from the group consisting of silver, aluminum, antimony, copper, iron, cobalt, nickel, thallium and zinc whereby to deposit a transparent coating of an oxide of a metal of said group upon a surface of the glass,

heating the glass to a temperature above about 400 F. but below the temperature at which the glass melts, and contacting the hot glass with a decomposable film-forming tin halide whereby to deposit a transparent electroconductive tin oxide coating upon a treated surface of the glass.

9. A method of providing a substantially hazefree glass base having a. transparent electroconductive coating thereon, which comprises heating a glass having the composition:

Alkali metal oxide of the group consisting of N320 and K20 Alkaline earth metal oxide of the group consisting of 10 to 35% by weight CaO and MgO '5 to 25% by weight the (3:10 content being at least 5% by Weight SiO- 50 to 75% by Weight A1 0; Up to 20% by weight to a temperature of above about 400 F. but below a temperature at which the glass melts, contacting the hot glass with a film-forming decomposable salt of a metal selected from the group consisting of silver, aluminum, antimony, copper, iron, cobalt, nickel, thallium and zinc whereby to deposit a transparent coating of an oxide of a metal of said group upon a surface of the glass, heating the glass to a temperature above about [3 400 F. but below the temperature at which the glass melts, and contacting the hot glass with a decomposable film-forming compound of a metal selected from the group consisting of indium, cadmium and tin whereby to deposit a transparent electroconductive coating of an oxide of a metal of said last named group upon a treated surface of the glass.

10. The method of claim 9 wherein the transparent metal oxide coating first formed on said glass is antimony oxide.

11. The method of claim 9 wherein the transparent metal oxide coating first formed on said glass is aluminum oxide.

12. The method of claim 9 wherein the transparent metal oxide coating first formed on said glass is silver oxide.

13. The method of claim 9 wherein the film- 14 forming compound of the metal of the group consisting of indium, cadmium and tin is a halide.

WILLIAM G. LYTLE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 10 Number Name Date 2,344,250 Jones Mar. 14, 1944 2,366,516 Geficken et a1. Jan. 2, 1945 2,429,420 McMaster Oct. 21, 1947 15 FOREIGN PATENTS Number Country Date 113,830 Australia Sept. 25, 1941 

9. A METHOD OF PROVIDING A SUBSTANTIALLY HAZEFREE GLASS BASE HAVING A TRANSPARENT ELECTROCONDUCTIVE COATING THEREON, WHICH COMPRISES HEATING A GLASS HAVING THE COMPOSITION: ALKALI METAL OXIDE OF THE GROUP CONSISTING OF NA2O ALKALINE EARTH METAL OXIDE OF THE GROUP CONSISTING OF TO A TEMPERATURE OF ABOVE ABOUT 400* F. BUT BELOW A TEMPERATURE AT WHICH THE GLASS MELTS, CONTACTING THE HOT GLASS WITH A FILM-FORMING DECOMPOSABLE SALT OF A METAL SELECTED FROM THE GROUP CONSISTING OF SILVER, ALUMINUM, ANTIMONY, COPPER, IRON, COBALT, NICKEL, THALLIUM AND ZINC WHEREBY TO DEPOSIT A TRANSPARENT COATING OF AN OXIDE OF A METAL OF SAID GROUP UPON A SURFACE OF THE GLASS, HEATING THE GLASS TO A TEMPERATURE ABOVE ABOUT 400* F. BUT BELOW THE TEMPERATURE AT WHICH THE GLASS MELTS, AND CONTACTING THE HOT GLASS WITH A DECOMPOSABLE FILM-FORMING COMPOUND OF A METAL SELECTED FROM THE GROUP CONSISTING OF INDIUM, CADMIUM AND TIN WHEREBY TO DEPOSIT A TRANSPARENT ELECTROCONDUCTIVE COATING OF AN OXIDE OF A METAL OF SAID LAST NAMED GROUP UPON A TREATED SURFACE OF THE GLASS. 